Lecture-5

Recapitulation of quantum formalism of the one electron (Hydrogen) atom

We have studied in the last semester, the problem of a one electron system like the Hydrogen
atom, a singly charged Helium ion or a doubly charged Lithium ion. All of these are two body
problems of a nucleus of charge (Ze) and an electron of charge (-e) interacting with each other
through the Coulomb force.

The Schrodinger equation of the problem is

𝑑 ℏ2 ℏ2 𝑧𝑒 2
𝑖ℏ 𝑑𝑡 𝜳(𝑟⃗1 , 𝑟⃗2 , 𝑡) = (− 2𝑚 ∇12 − 2𝑚 ∇22 − 4𝜋𝜖 ) 𝜳(𝑟⃗1 , 𝑟⃗2 , 𝑡) … … (1.1)
𝑁 𝑒 0 |𝑟⃗2 −𝑟⃗1 |

Where, mN and me are the mass of the nucleus and the electron positioned at 𝑟⃗1 and 𝑟⃗2 respectively.
AS the potential energy for that reason the Hamiltonian is independent of time, using principle of
separation of variable (as dis cussed in the first lecture) can be separated to two equations one
dealing with space coordinated and the other time

ℏ2 ℏ2 𝑧𝑒 2
(− ∇2 − ∇2 − ) 𝛹(𝑟⃗1 , 𝑟⃗2 ) = 𝐸 𝛹(𝑟⃗1 , 𝑟⃗2 ) …… (1.2)
2𝑚𝑁 1 2𝑚𝑒 2 4𝜋𝜖0 |𝑟⃗2 −𝑟⃗1 |

𝑑
And 𝑖ℏ 𝑑𝑡 𝑓(𝑡) = 𝐸𝑓(𝑡)

The combined wave function 𝜳(𝑟⃗1 , 𝑟⃗2 , 𝑡) = 𝛹(𝑟⃗1 , 𝑟⃗2 )𝑓(𝑡)

Equation (1.2) is the time independent stationary state equation. It involves six coordinates and the
differential equation is not amenable to solution till we separate it in to single variables

In the process, first we separate the two body problem to relative and centre of mass coordinate
𝑚𝑒 𝑥2 +𝑚𝑁 𝑥1
Relative coordinate 𝑥 = 𝑥2 − 𝑥1 and centre of mass coordinate 𝑋 = 𝑀

where 𝑀 = 𝑚𝑁 + 𝑚𝑒 total mass of atom

𝜕 𝜕 𝑑𝑥 𝜕 𝑑𝑋 𝜕 𝑚𝑁 𝜕
Now 𝜕𝑥1
= 𝜕𝑥 𝑑𝑥 + 𝜕𝑋 𝑑𝑥 = − 𝜕𝑥 + 𝑀 𝜕𝑋
1 1

1 𝜕2 1 𝜕 𝑚𝑁 𝜕 𝜕 𝑚𝑁 𝜕 1 𝜕2 2 𝜕 𝜕 𝑚𝑁 𝜕 2
And = (− + ) (− + ) = − +
𝑚𝑁 𝜕𝑥12 𝑚𝑁 𝜕𝑥 𝑀 𝜕𝑋 𝜕𝑥 𝑀 𝜕𝑋 𝑚𝑁 𝜕𝑥 2 𝑀 𝜕𝑥 𝜕𝑋 𝑀 2 𝜕𝑋 2

𝜕 𝜕 𝑑𝑥 𝜕 𝑑𝑋 𝜕 𝑚𝑒 𝜕
Similarly = + = +
𝜕𝑥2 𝜕𝑥 𝑑𝑥2 𝜕𝑋 𝑑𝑥2 𝜕𝑥 𝑀 𝜕𝑋

1 𝜕2 1 𝜕 𝑚𝑒 𝜕 𝜕 𝑚𝑒 𝜕 1 𝜕2 2 𝜕 𝜕 𝑚𝑒 𝜕 2
And = ( + )( + ) = + +
𝑚𝑒 𝜕𝑥22 𝑚𝑒 𝜕𝑥 𝑀 𝜕𝑋 𝜕𝑥 𝑀 𝜕𝑋 𝑚𝑒 𝜕𝑥 2 𝑀 𝜕𝑥 𝜕𝑋 𝑀 2 𝜕𝑋 2

Adding the two equations we

1 𝜕2 1 𝜕2 1 𝜕2 2 𝜕 𝜕 𝑚𝑁 𝜕 2 1 𝜕2 2 𝜕 𝜕 𝑚 𝜕2 1 1 𝜕2 1 𝜕2
𝑚𝑁 𝜕𝑥12
+𝑚 2 =𝑚 2 − 𝑀 𝜕𝑥 𝜕𝑋 + 𝑀 2 𝜕𝑋 2
+𝑚 2 + 𝑀 𝜕𝑥 𝜕𝑋 + 𝑀2𝑒 𝜕𝑋 2 = (𝑚 + 𝑚 ) 𝜕𝑥 2 + 𝑀 𝜕𝑋 2
𝑒 𝜕𝑥2 𝑁 𝜕𝑥 𝑒 𝜕𝑥 𝑁 𝑒
 1 𝜕2 1 𝜕2 1 𝜕2 1 𝜕2
+ = +
𝑚𝑁 𝜕𝑥12 𝑚𝑒 𝜕𝑥22 𝜇 𝜕𝑥 2 𝑀 𝜕𝑋 2
1 1 1 𝑚 𝑚
Where reduced mass 𝜇 is defined as 𝜇 = 𝑚 + 𝑚 or 𝜇 = 𝑚 𝑁+𝑚𝑒
𝑁 𝑒 𝑁 𝑒

1 1 1 1
Extending to three dimensions, we can write ∇2
𝑚𝑁 1
+ 𝑚 ∇22 = 𝜇 ∇2𝑥 + 𝑀 ∇𝑋2
𝑒

Using this relation, the Schrodinger equation (1.2) in the relative and centre of mass coordinate can
be written as:

ℏ2 2 ℏ2 2 𝑧𝑒 2
(− ∇𝑥 − ∇𝑋 − ) 𝛹(𝑟⃗, 𝑅⃗⃗ ) = 𝐸 𝛹(𝑟⃗, 𝑅⃗⃗ )
2 2𝑀 4𝜋𝜖0 𝑟

1 1 −1
Where reduced mass 𝜇 = (𝑚 + 𝑚 ) and 𝑀 = 𝑚𝑒 + 𝑚𝑁 , Relative coordinate 𝑟⃗ = 𝑟⃗2 − 𝑟⃗1 and
𝑒 𝑁
𝑚 𝑟⃗ +𝑚 𝑟⃗
centre of mass coordinate 𝑅⃗⃗ = 𝑒 2 𝑀 𝑁 1

As the Hamiltonian do not contain any cross term involving both x and X coordinate, the two body
problem can be reduced to two one body problems in the relative coordinates and the centre of
mass coordinates using the separation of variable principle as:

ℏ2 2 𝑧𝑒 2
(− ∇𝑥 − ) 𝜓(𝑟⃗) = 𝜀 𝜓(𝑟⃗) …. (1.3)
2𝜇 4𝜋𝜖0 𝑟

ℏ2 2
And − ∇ 𝜓𝑐𝑚 (𝑅⃗⃗) = 𝜀𝑐𝑚 𝜓𝑐𝑚 (𝑅⃗⃗ )
2𝑀 𝑋

𝛹(𝑟⃗, 𝑅⃗⃗ ) = 𝜓(𝑟⃗)𝜓𝑐𝑚 (𝑅⃗⃗) and 𝐸 = 𝜀 + 𝜀𝑐𝑚

For determination of the energy and wave function of the corresponding orbitals, we need to solve
the one body Schrodinger equation in the relative coordinates as given in Eqn(1.3). The equation
corresponding to centre of mass only involve kinetic energy of motion of the atom as a whole in
space.

The potential energy being spherically symmetric, the equation (1.3) need to be solved using
spherical polar coordinates

ℏ2 1 𝑑 2 𝑑 1 𝜕 𝜕 1 𝜕2 𝑧𝑒 2
[− ( 2 𝑟 + 2 𝑠𝑖𝑛𝜃 + 2 2 ) − ] 𝜓(𝑟, 𝜃, 𝜑) = 𝜀 𝜓(𝑟, 𝜃, 𝜑)
2𝜇 𝑟 𝑑𝑟 𝑑𝑟 𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑟 𝑠𝑖𝑛 𝜃 𝜕𝜑2 4𝜋𝜖0 𝑟

Multiply above equation by 2𝜇𝑟 2

𝑑 2 𝑑 1 𝜕 𝜕 1 𝜕2 𝑧𝑒 2 2𝜇𝑟 2
[−ℏ2 ( 𝑟 + 𝑠𝑖𝑛𝜃 + ) − ] 𝜓(𝑟, 𝜃, 𝜑) = 𝜀2𝜇𝑟 2 𝜓(𝑟, 𝜃, 𝜑)
𝑑𝑟 𝑑𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃 𝜕𝜑2 4𝜋𝜖0 𝑟

Rearranging the radial and angular coordinates separately, we can write

 𝑑 2 𝑑 𝑧𝑒 2 𝑟 2 2𝜇 1 𝜕 𝜕 1 𝜕2
[{−ℏ2 𝑟 − − 2𝜇𝜀𝑟 2 } − ℏ2 ( 𝑠𝑖𝑛𝜃 + )] 𝜓(𝑟, 𝜃, 𝜑) = 0
𝑑𝑟 𝑑𝑟 4𝜋𝜖0 𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃 𝜕𝜑2

As the first bracket do not contain any angular coordinate and second bracket do not contain any
radial coordinate, the equation can be separated in to the radial and angular parts using separation
of variable principle as

ℏ2 1 𝑑 𝑑 𝜆 𝑧𝑒 2
[− 2𝜇 (𝑟2 𝑑𝑟 𝑟 2 𝑑𝑟 − 𝑟2 ) − 4𝜋𝜖 𝑟] 𝑅(𝑟) = 𝜀 𝑅(𝑟) … (1.4)
0

1 𝜕 𝜕 1 𝜕2
−ℏ2 (𝑠𝑖𝑛𝜃 𝜕𝜃 𝑠𝑖𝑛𝜃 𝜕𝜃 + 𝑠𝑖𝑛2 𝜃 𝜕𝜑2 ) 𝑌(𝜃, 𝜑) = 𝜆ℏ2 𝑌(𝜃, 𝜑) … (1.5)

Where , the wave function 𝜓(𝑟⃗) = 𝜓(𝑟, 𝜃, 𝜑) = 𝑅(𝑟)𝑌(𝜃, 𝜑) …(1.6)

The operator in the left side of the equation(1.5) represent the square of angular momentum L2

[The radial wave function 𝑅(𝑟) is not to be confused with the centre of mass coordinate 𝑅⃗⃗]

Multiplying Eqn (1.5) with 𝑠𝑖𝑛2 𝜃, we obtain

𝜕 𝜕 𝜕2
−ℏ2 ({𝑠𝑖𝑛𝜃 𝑠𝑖𝑛𝜃 + 𝜆𝑠𝑖𝑛2 𝜃} + { 2 }) 𝑌(𝜃, 𝜑) = 0
𝜕𝜃 𝜕𝜃 𝜕𝜑

The first curly brackets have operators in 𝜃 and the second only involve 𝜑 and hence can be
separated by separation of variable principle as

1 𝜕 𝜕 𝜐
−ℏ2 ( 𝑠𝑖𝑛𝜃 − ) 𝛩(𝜃) = 𝜆ℏ2 𝛩(𝜃) …(1.7)
𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃

𝜕2
and − 𝜕𝜑2 𝜙(𝜑) = 𝜐𝜙(𝜑) …(1.8)

The wave function of the angular part 𝑌(𝜃, 𝜑) = 𝛩(𝜃)𝜙(𝜑) …(1.9)

The differential equations (1.4),(1.7) and (1.8) deal with single coordinate and r, θ and ϕ respectively
and can be solved easily

Here it is important to note that the operator on the left side of eqn(1.5) and (1.8)represent the
operators L2 and (Lz)2 respectively.

𝑑
𝐿𝑧 = −𝑖ℏ
𝑑𝜑

We will not venture here to solve these equations of the hydrogen atom Schrodinger equation as
these are being elaborately discussed in the last semester.
1
The solution of equation (1.8)is straight forward and appears as 𝜙(𝜑) = 𝑒 𝑖√𝜐𝜑
√2𝜋

and using the boundary condition 𝜙(𝜑) = 𝜙(2𝜋 + 𝜑)

one obtain the value of 𝜐 = 𝑚2 , where m can take positive , negative integer or zero.
 1
Hence the solution of 𝜑part is 𝜙𝑚 (𝜑) = 𝑒 𝑖𝑚𝜑 and the eigenvalue of Lz Is
√2𝜋

𝑑 𝑑 1 𝑖𝑚𝜑 1 𝑖𝑚𝜑
𝐿𝑧 𝜙𝑚 (𝜑) = −𝑖ℏ 𝜙𝑚 (𝜑) = −𝑖ℏ 𝑒 = 𝑚ℏ 𝑒 = 𝑚ℏ𝜙𝑚 (𝜑)
𝑑𝜑 𝑑𝜑 √2𝜋 √2𝜋

Substituting in Eqn (1.7) , the equation dealing with the variable 𝜃 appears as:

1 𝑑 𝑑 𝑚2
−ℏ2 (𝑠𝑖𝑛𝜃 𝑑𝜃 𝑠𝑖𝑛𝜃 𝑑𝜃 − 𝑠𝑖𝑛2 𝜃) 𝛩(𝜃) = 𝜆ℏ2 𝛩(𝜃)

This equation is solved using the same principles like change of variable, asymptotic solution
and then series solution.

First changing the variable to 𝜔 = cos 𝜃, and writing 𝛩(𝜃) = 𝑃(𝜔) the equation appears
as:

𝑑 𝑑𝑃 𝑚2
(1 − 𝜔2 ) + (𝜆 − )𝑃 = 0
𝑑𝜔 𝑑𝜔 1 − 𝜔2

Using the series solution , it can be shown that the solution exists when 𝜆 = 𝑙(𝑙 + 1) and
the corresponding wave function is the associated Legendre polynomial 𝑃𝑙𝑚 (𝜔) with a normalization
constant
1
(2𝑙 + 1) (𝑙 − 𝑚)! 2 𝑚
𝑃=[ ] 𝑃𝑙 (cos 𝜃)
2 (𝑙 + 𝑚)!
1 |𝑚|
|𝑚| 𝑑
Where 𝑃𝑙𝑚 (𝜔) = (1 − 𝜔2 )2 𝑃 (𝜔)
𝑑𝜔 |𝑚| 𝑙

𝑃𝑙 (𝜔) is the LegendrePolynomial of order l and can be determined from the Generating
function
∞
(1 − 2𝑠𝜔 + 𝑠 2 )−1/2 = ∑ 𝑠 𝑙 𝑃𝑙 (𝜔)
𝑙=0

On expanding we obtain

1 1 3 1 1 3 5 1
1 + (− ) (−2𝑠𝜔 + 𝑠 2 ) + (− ) (− ) ( ) (−2𝑠𝜔 + 𝑠 2 )2 + (− ) (− ) (− ) ( ) (−2𝑠𝜔 + 𝑠 2 )3
2 2 2 2 2 2 2 6
+ ⋯ = 𝑃0 (𝜔) + 𝑠𝑃1 (𝜔) + 𝑠2 𝑃2 (𝜔) + 𝑠3 𝑃3 (𝜔)

(3𝜔2 − 1) 3 (5𝜔3 − 3𝜔)

1 + 𝑠𝜔 + 𝑠 2 +𝑠 + ⋯ = 𝑃0 (𝜔) + 𝑠𝑃1 (𝜔) + 𝑠2 𝑃2 (𝜔) + 𝑠3 𝑃3 (𝜔) + ⋯
2 2
(3𝜔2 −1) (5𝜔3 −3𝜔)
𝑃0 (𝜔) = 1, 𝑃1 (𝜔) = 𝜔, 𝑃2 (𝜔) = , 𝑃3 (𝜔) =
2 2

Associated Legendre polynomials are

𝑃10 (𝜔) = 𝑃0 (𝜔) = 1,

 1 𝑑 1 𝑑 1
𝑃11 (𝜔) = (1 − 𝜔2 )2 𝑃1 (𝜔) = (1 − 𝜔2 )2 𝜔 = (1 − 𝜔2 )2 = sin 𝜃
𝑑𝜔 𝑑𝜔

𝑃10 (𝜔) = (1 − 𝜔2 )0 𝑃1 (𝜔) = 𝜔 = cos 𝜃

1
|−1| 𝑑 |−1| 1 𝑑 1
𝑃1−1 (𝜔) = (1 − 𝜔2 )2 −1
𝑃1 (𝜔) = (1 − 𝜔2 )2 𝜔 = (1 − 𝜔2 )2 = sin 𝜃
𝑑𝜔 𝑑𝜔

So the solution of the angular part which is equal to the operator L2 as given by Equation
(1.5) are the spherical Harmonics 𝑌𝑙𝑚 (𝜃, 𝜑), which can be written as

1 𝜕 𝜕 1 𝜕2
𝐿2 𝑌𝑙𝑚 (𝜃, 𝜑) = −ℏ2 (𝑠𝑖𝑛𝜃 𝜕𝜃 𝑠𝑖𝑛𝜃 𝜕𝜃 + 𝑠𝑖𝑛2 𝜃 𝜕𝜑2) 𝑌(𝜃, 𝜑) = 𝑙(𝑙 + 1)ℏ2 𝑌𝑙𝑚 (𝜃, 𝜑)

1
(2𝑙 + 1) (𝑙 − 𝑚)! 2 𝑚
𝑌𝑙𝑚 (𝜃, 𝜑) = [ ] 𝑃𝑙 (cos 𝜃)𝑒 𝑖𝑚𝜑
4𝜋 (𝑙 + 𝑚)!

The solution of the angular part is the spherical harmonics 𝑌𝑙𝑚 (𝜃, 𝜑) and on substituting
the value of λ = 𝑙(𝑙 + 1) , the radial part [equation (1.4)] appears as

ℏ2 1 𝑑 𝑑 𝑙(𝑙+1) 𝑧𝑒 2
[− 2𝜇 (𝑟 2 𝑑𝑟 𝑟 2 𝑑𝑟 − ) − 4𝜋𝜖 𝑟] 𝑅(𝑟) = 𝜀 𝑅(𝑟)
𝑟2 0

On solving the above equation, using the same principles like change of variable,
asymptotic solution and then series solution , it is found that the series terminates for terms
with highest power of r = n’, the radial quantum number and that the energy is found to
depend on the principle quantum number n which is related to the radial quantum number
n and the orbital (Azimuthal) quantum number l as 𝑛 = 𝑛′ + 𝑙 + 1 where both n and l can
take integer values from 0 to n-1. The expression for the bound state energy appears as

ℏ2 𝑍 2 𝜇𝑍 2 𝑒 4
𝜀𝑛 = − 2𝜇𝑎2 𝑛2 = − 8𝜖2ℎ2 𝑛2 ;
0 0

4𝜋𝜖0 ℏ2
Where, the Bohr radius 𝑎0 = 𝜇𝑒 2

The radial and the angular wave functions Takes the form:

2𝑍 3 (𝑛 − 𝑙 − 1)! −𝑛𝑎
𝑍𝑟 2𝑍𝑟 𝑙 2𝑙+1 2𝑍𝑟
𝑅𝑛𝑙 (𝑟) = √( ) 𝑒 0 ( ) 𝐿𝑛−𝑙−1 ( )
𝑛𝑎0 2𝑛{(𝑛 − 𝑙)!}3 𝑛𝑎0 𝑛𝑎0

(2𝑙 + 1)(𝑙 − 𝑚)! 𝑚

𝑌𝑙𝑚 (𝜃, 𝜑) = √ 𝑃 (𝑐𝑜𝑠𝜃)𝑒 𝑖𝑚𝜑
4𝜋 (𝑙 + 𝑚)! 𝑙
Where, 𝐿2𝑙+1 𝑚
𝑛+𝑙 (𝜌) and 𝑃𝑙 (𝑐𝑜𝑠𝜃) are the associate Laguerre polynomial and associate
Legendre Polynomial respectively and appears as: m is the magnetic quantum number and
can take values from –l to +l in integer steps.

𝑒 𝑥 𝑥 −𝑘 𝑑 𝑛 −𝑥 𝑛+𝑘
𝐿𝑘𝑛 (𝑥) = (𝑒 𝑥 )
𝑛! 𝑑𝑥 𝑛
(−1)𝑚 𝑚 𝑑 𝑚+𝑙
𝑃𝑙𝑚 (𝑥) = (1 − 𝑥 2) 2 (𝑥 2 − 1)𝑙
2𝑙 𝑙! 𝑑𝑥 𝑚+𝑙
So we have come across four quantum numbers

n ⇒ Principle Quantum Number

n⇒ radial quantum number

𝑙 ⇒Azimuthal Quantum Number takes integer values

m ⇒ Magnetic Quantum Number and takes values between – 𝑙 to + 𝑙 in integer steps

However, as n depends on n and 𝑙 through the relation 𝑛 = 𝑛′ + 𝑙 + 1, only the three

quantum numbers n, 𝑙 and m remain independent and are considered for designating
the states.

For all systems with spherically symmetric potential each sate designated by the
quantum number 𝑙 is (2 𝑙 +1)fold degenerate as the quantum number m takes values
from – 𝑙 to + 𝑙 in integer steps .

Further for the one electron atom/ions, where we have central potential, the n state is n
fold degenerate as 𝑙 takes values from 0 to n -1 in integer steps.

Hence for a central potential the n state have a degeneracy of ∑𝑛−1

𝑙=0 (2𝑙 + 1) = 𝑛
2

If 2 fold spin degeneracy is taken in to account, the maximum possible occupancy in the
state n equals 2n2.
The possible quantum numbers and degeneracy for the Hydrogen atom is tabulated

Maximum Energy
occupancy (eV)
n n’ 𝑙 m degeneracy
(with spin
consideration)
1 0 0(s) 0 1 2 -13.6 eV
1 0(s) 0
1
2 4 8 -3.4 eV
0 1(p) 0
-1
2 0(s) 0
1
1 1(p) 0
-1
3 2 9 18 -1,51 eV
1
0 2(d) 0
-1
-2

We list the radial function Rnl (r) the spherical harmonics Ylm and the wave function ψnlm for the
states corresponding to the quantum numbers n=1 and 2

𝑍 3/2 1 1 𝑍 3/2
𝑅10 (𝑟) = 2 (𝑎 ) 𝑒 −𝑍𝑟/𝑎0 , 𝑌00 (𝜃, 𝜑) = , 𝜓100 = ( ) 𝑒 −𝑍𝑟/𝑎0
0 √4𝜋 √𝜋 𝑎0

3 3
1 𝑍 2 𝑍𝑟 1 1 𝑍 2 𝑍𝑟
𝑅20 (𝑟) = ( ) (1 − 2𝑎 ) 𝑒 −𝑍𝑟/2𝑎0 , 𝑌00 (𝜃, 𝜑) = , 𝜓200 = ( ) (1 − 2𝑎 ) 𝑒 −𝑍𝑟/2𝑎0
√2 𝑎0 0 √4𝜋 √8𝜋 𝑎0 0

3 3
1 𝑍 2 𝑍𝑟 −𝑍𝑟/2𝑎 3 1 𝑍 2 𝑍𝑟 −𝑍𝑟/2𝑎
𝑅21 (𝑟) = ( ) 𝑒 0 , 𝑌10 (𝜃, 𝜑) = √4𝜋 𝑐𝑜𝑠𝜃 , 𝜓210 = √32𝜋 (𝑎 ) 𝑒 0 𝑐𝑜𝑠𝜃
√24 𝑎0 𝑎0 0 𝑎0

3
3 ±𝑖𝜑 1 𝑍 2 𝑍𝑟 −𝑍𝑟/2𝑎
𝑌1 ±1 (𝜃, 𝜑) = √ 𝑠𝑖𝑛𝜃 𝑒 , 𝜓2 1 ±1 = ∓√ ( ) 𝑒 0 𝑠𝑖𝑛𝜃 𝑒 ±𝑖𝜑
8𝜋 64𝜋 𝑎0 𝑎0
The radial wave function Rnl (r) and the radial probability density [𝑟 2 |𝑅𝑛𝑙 |2 ] for few of the lower
states of hydrogen atom are shown in the figure .

In the 1s radial probability density peak of 1s state occur at a0 , which is the same as Bohr radius
and the peak value is 0.54. ⇒ There is no node for 1s state. ⇒ The probability density goes to zero
at r = 0, it means that the probability of finding the electron at the nucleus is zero.

The 2s radial probability density has two peaks: one at 0.76 a0 and next one at 5.24 a0. The height of
the peak nearest to the nucleus is much smaller than that of the outer peak. The presence of a small
peak near the origin is called penetration.

With these information on the atomic orbitals of hydrogen like one electron atom/ions, we will
proceed in the next class to discuss the two electron Helium atom.
In this lecture we have setup the Schrodinger equation for the two body(nucleus and electron)
problem.

Separated in to two one body equations : the relative coordinate and the centre of mass eqn

The potential being spherically symmetric , the relative equation is written in spherical polar
coordinates and separated to two equations one involving the radial coordinate and the other
dealing with angular coordinate.

The angular coordinate equation is again resolved in to single coordinate equations in θ and ϕ

On solving the ϕ part, we obtain the dependence on the quantum number m ( which is generally
known as magnetic quantum number)

The solution of θ part depends on the quantum numbers l and m ; l being the orbital angular
momentum quantum number

The solution of the angular part as a whole is the spherical harmonics 𝑌𝑙𝑚 (𝜃, 𝜑)

The solution of the radial part depends on the quantum numbers n and l; n being the principal
quantum number and is equal to 𝑛 = 𝑛′ + 𝑙 + 1; 𝑛′ being the radial quantum number.

The energy of the bound state depend on the quantum number n only. The state n is n fold
degenerate corresponding to n values of 𝑙 which takes values between 0 to n-1 in integer steps. This
degeneracy is a consequence of Coulomb potential.

Each level designated by 𝑙 is 2 𝑙 +1 fold degenerate corresponding to 2 𝑙 +1 values of m which takes

values between −𝑙 to 𝑙 in integer steps. This degeneracy is a consequence of central spherically
symmetric potential.

Hence each state n in the Coulomb potential is n2 fold degenerate with maximum occupancy of 2 n2

after taking the two fold spin degeneracy in to account.

Each orbital is designated by the three quantum numbers n, 𝑙 and m

The wave functions for some of the orbitals are provided, the radial function and the associated
radial probability density is depicted for some of the orbitals.